Synthesis of arylene bis-silanols

ABSTRACT

This invention is directed to the preparation of certain arylene bis-silanols in highly purified form and to the preparation of five new arylene bis-silanols in particular, along with a procedure for polymerizing these and other arylene-type bis-silanols using phosgene as a polymerization promotor or catalyst, to obtain highly purified, high molecular weight arylene-siloxanylene polymers having the characteristic structure: ##STR1## where Y is an arylene or substituted arylene moiety; R and R&#39; are the same or different alkyl group(s), substituted alkyl group(s) or a phenyl group, x ranges from about 1 to 3 and n ranges from about 300 to 1500, said polymers having molecular weights (number average) of 100,000 and higher. 
     Preferred polymers are those arylenesiloxanylenecarbonate polymers which, when laminated to polycarbonate sheets or glass maintain their transparency, stability and adherence to said substrates at temperatures of up to and including 400° F. Such polymers are useful for the formulation of high temperature interlayers for windshields and canopies for aircraft and related aerospace vehicles.

RIGHTS OF THE GOVERNMENT

The invention described herein may be manufactured and used by or forthe Government of the United States for all governmental purposeswithout payment of any royalty.

BACKGROUND OF THE INVENTION AND PRIOR ART

Prior to this invention, polysiloxanylenes containing recurring arylenebackbone groups and particularly arylene backbone groups containingcarbonate moieties, have not been successfully prepared in highmolecular weights, viz., in molecular weights of 100,000 and above. Sucharylenesiloxanylene polymers, prepared in accordance with prior artprocedures, have demonstrated considerably lower molecular weights, andrelatively poor physical and mechanical properties. These prior artpolymers have no established practical application.

The polyarylenesiloxanylenes of the present invention are polymershaving the characteristic structural formula: ##STR2## where Y is anarylene or substituted arylene moiety, preferably one which additionallycontains a carbonate group; R and R' are the same or different alkylgroup(s), substituted alkyl group(s) or a phenyl group, and arepreferably lower alkyl or substituted lower alkyl groups containing from1 to 3 carbon atoms; x ranges from about 1 to 3; and n ranges from 300to 1500, said polymers having molecular weights (number average) of100,000 and higher. This structural formula is referred to hereinafteras Formula A. The present invention permits the synthesis of highly purearylene bis-silanol monomers and their polymerization in the presence ofphosgene and an aromatic heterocyclic amine inert to reaction withphosgene, e.g., pyridine, methyl pyridine, cholidines and the like, toobtain high molecular weight homopolymers and copolymers, many of whichare transparent, exhibit good adhesion to polycarbonates and glass andcan withstand temperatures as high as 400° F. without degradation.Characteristically, the arylene-siloxanylene polymers, including thosecontaining organocarbonate groups, prepared in accordance with thisinvention, exhibit viscosities beyond one deciliter per gram (1 dl/g).Additionally, these polymers display good mechanical properties forpractical applications. The polymers of this invention provide basematerials for high temperature-resistant, optically-transparentelastomers suitable for use in such applications as interlayer sheetmaterials for the fabrication of laminated safety-glass-type aircraftwindshields and canopy assemblies.

The present invention relates to the syntheses of highly purifiedbis-silanols, such as, bis[(4-hydroxydimethylsilyl)phenyl]carbonate,bis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate,bis(3-hydroxydimethylsilylphenyl)carbonate,bis[3-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate,bis[4-(1-hydroxy-1,1,3,3-tetramethyldisloxanyl)]benzene and theirpolymerization with phosgene (carbonyl chloride) to form high molecularweight siloxanylene polymers.

The highly pure bis-silanols obtained in accordance with this inventionare essential in the synthesis of the desired high molecular weightsiloxanylene polymers. It is well known that silanols, especially in thepresence of a catalytic amount of acid or base, or at a hightemperature, undergo condensation reactions to form siloxanes inaccordance with the following equation:

    .tbd.Si--OH+.tbd.Si--OH→.tbd.Si--O--Si.tbd.+HOH

Thus, in the prior preparation of arylene bis-silanols, siloxanes wereusually formed. This reaction not only consumed the synthesizedsilanols, but the siloxane formed an oily mixture with the silanol,which mixture, in many cases could not be separated adequately. As aresult of the aforementioned side reaction, many silanols which havebeen prepared by existing literaure methods are virtually impurecompounds and tend to form only low molecular weight polysiloxanes whenpolymerized.

In accordance with the present invention, however, purebis(4-hydroxydimethylsilylphenyl)carbonate andbis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate,together with its corresponding meta analog, were prepared starting withthe 3- or 4-bromophenol.

Although certain of the reactions which were utilized to prepare selectmonomers in accordance with a new five (or seven)-step synthesis for theproduction of high molecular weight, carbonate-containing, arylenesiloxanylene polymers of this invention are based on reactions indicatedin Lloyd, et al., U.S. Pat. No. 3,595,974 and Mironov, et al., U.S. Pat.No. 3,697,569; the procedures indicated in these Lloyd, et al., andMironov, et al., patents were found inadequate for providingintermediates and monomers of the high purity required to obtain thehigh molecular weight polymers of this invention. For example,4-dimethylsilylphenol, the preparation of which is identified hereinbelow in the detailed description of the invention as Step 3, wasreported by Mironov in U.S. Pat. No. 3,697,569 to melt at 35° to 37° C.However, 4-dimethylsilylphenol was isolated by the present inventors asa compound melting at 61° C.

Similarly, although Lloyd, et al., U.S. Pat. No. 3,595,974 disclosed thepreparation of several silylphenyl carbonate intermediates, theprocedures disclosed fail to result in obtaining any purebis[(4-hydroxydimethylsilyl)phenyl]carbonate. This is in sharp contrastwith the synthesis procedure of this invention which results at eachstage in a product which could be isolated in a high state of purity.

The preparation of siloxane-containing polymers containing carbonate andpolysiloxy blocks has been reported in U.S. Pat. No. 2,999,845, issuedto Goldberg. This Goldberg patent is directed to the preparation of suchblock copolymers by reacting dihydric phenols with a carbonate ester,and dimethyldichlorosilane. Although the Goldberg patent utilizes aphosgenation step in pyridine in the course of preparing the referencedGoldberg polymers for the generation of the carbonate linkages, no suchreaction occurs in the present invention. It will be apparent that thespecific polymerization step of this invention, using the phosgene inthe presence of an aromatic heterocyclic amine inert to reactiontherewith, e.g., pyridine, for obtaining the highly purified polymers,is readily distinguishable from the Goldberg patent and the other priorart mentioned herein in that the phosgene does not react to form suchlinkages. The block copolymers formed in accordance with this Goldbergpatent contain hydrolytically unstable phenoxy-silyl bonds in thepolymer backbone structure. No such bonds are present in the polymers ofthis invention. The Goldberg phosgenation process for polymerizationuses phosgene to form carbonate linkages whereas in this inventionphosgene is used to promote the formation of siloxane linkages (probablyby dehydrating silanols or acting as a polymerization catalyst topromote formation of siloxane bonds).

U.S. Pat. No. 3,832,419 issued to Merritt, Jr., is directed to thepreparation of organopolysiloxane-polycarbonate block copolymers fromhalogen chain-stopped organopolysiloxane, dihydric phenol and phosgenein a process which uses ammonia as an acid acceptor in the initialdihydric phenol/halogen chain-stopped organopolysiloxane reaction. Thisreaction is then followed by phosgenation to form the copolymersapparently in a manner similar to Goldberg U.S. Pat. No. 2,999,845.Nowhere does Merritt, Jr. teach preparation of polysiloxanylene arylenecarbonates.

BRIEF SUMMARY OF THE INVENTION

This invention is directed to the preparation of arylene bis-silanols inhighly purified form having the general formula ##STR3## wherein Y is##STR4## R and R' are the same or different alkyl group(s), substitutedalkyl group(s) or a phenyl group, and are preferably lower alkyl orsubstituted lower alkyl groups containing from 1 to 3 carbon atoms, R"is H, methyl or trifluoromethyl; and x is an integer having a value of 0or 1 and polymerization of said bis-silanols in an aromatic heterocyclicamine inert to reaction with phosgene, e.g., pyridine solution, by theuse of phosgene to obtain readily isolatable, high molecular weightpolymers having the following structure: ##STR5## where x can range from1 to 3, where n can range from about 300 to about 1500 and more usuallyranges from about 500 to 850. Typical R and R' groups include methyl,ethyl, vinyl, propyl, isopropyl, phenyl and the like, includinghalogen-substituted R and R', such as, for example,3,3,3-trifluoropropyl.

It is also possible, according to the process of this invention toproduce copolymers by combining a co-monomer with the above-describedarylene bis-silanol monomer and thereafter treat the blend of monomerand co-monomer with phosphene in the presence of the aforesaid aromaticheterocyclic amine. Such co-monomer has the same general formula as thatgiven above, but differs from the monomer. Preferably, the co-monomerhas a vinyl group in at least one of the R or R' positions. The ratio ofmonomer to co-monomer may be in the approximate range of 10:1 to 1:10.

It will be observed that in some of the polymers of this invention, thepolymer's backbone structure will not contain the carbonate linkage eventhough phosgene is employed in the polymerization step. The phosgeneherein acts essentially as a polymerization catalyst to promoteinformation of siloxane linkages (probably by dehydration of thebis-silanols).

These arylene bis-silanols are prepared by various procedures leading tothe preparation of arylene bis-hydride precursors which are converted tothe corresponding bis-hydroxy compounds by a catalytic oxidation-typereaction.

Novel carbonate-containing arylene bis-silanols are obtained byprocedures involving a 5- (or 7-) step reaction sequence starting withbromophenols. The bromophenols are converted to siloxybromobenzenederivatives, which are then successively reacted to form phenoxysilylhydrides, silylphenols, bis-silylphenylcarbonates, and finallybis-hydroxyphenylcarbonates.

The thus synthesized arylene bis-silanol monomers are then polymerizedwith phosgene, viz., carbonyl chloride, in the presence of the aforesaidtype of aromatic heterocyclic amine to yield the desired high molecularweight polymers of this invention.

DETAILED DESCRIPTION OF THE INVENTION

According to the present invention, there are synthesized highlypurified arylene bis-silanols, and especially carbonate-containingmonomers, such as bis(4-hydroxydimethylsilylphenyl)carbonate;bis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate;bis(3-hydroxydimethylsilylphenyl)carbonate;bis[3-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate andbis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)]benzene, which arepolymerized by use of phosgene to form high molecular weightarylenesiloxanylene polymers.

While the demonstrative 5-step synthesis and polymerization descriptionherein below is given specifically in respect of the synthesis ofbis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate and itspolymerization by the use of phosgene, it should be observed that any ofthe previously mentioned carbonate-containing arylene bis-silanols canlikewise be synthesized and polymerized in accordance with suchprocedures.

STEP 1 Preparation of 4-bromophenoxydimethyldisilane

To a solution of 346.0 g (2.0 mol) of 4-bromophenol in 400 ml of toluenewas added slowly 140.0 g (1.05 mol) of 1,1,3,3-tetramethyldisilazane.After the addition was complete, the reaction mixture was heated toreflux for 3 hours. After toluene was removed by evaporation undernitrogen, vacuum distillation at 2 mm/85°-95° C. gave 328.0 g (71%) ofthe expected compound, nmr; δ, 0 (d, 6, SiCH₃); 4.6 (septet, 1, SiH);6.6 (m, 4.2, φH).

STEP 2 Preparation of 4-dimethylsilylphenoxydimethylsilane

To a three-necked 2-l flask containing 37.0 g (1.52 mol) of magnesium,94.0 g (1 mol) of dimethylchlorosilane and 100 ml of freshly-distilledtetrahydrofuran was added slowly and under nitrogen a solution of 328.0g (1.42 mol) of 4-bromophenoxydimethylsilane and 94.0 g (1 mol) ofdimethylchlorosilane. During the addition, the reaction temperature waskept at 40°-50° C. After the addition was complete, the reaction mixturewas refluxed and part of the tetrahydrofuran was removed bydistillation. After cooling, the inorganic salt was precipitated bypetroleum ether (b.p. 30°-60° C.) and filtered. The filtrate wasconcentrated on a rotary evaporator and then vacuum distilled. Theexpected compound (234.0 g, 78.5%) distilled at 85°-95° C./3.5 mm.

Calcd. for C₁₀ H₁₈ O Si₂ O: C, 57.06; H, 8.62; Si, 26.71; mol wt 210.33.Found: C, 57.10; H, 8.69; Si, 25.80; mol wt. 234.00 (VPO).

nmr; δ, 0 (m, 13, SiCH₃); 4.17 (septet, 1, SiH) 4.76 (septet, 1, SiH);6.6-7.17, (m, 4.3, φH).

STEP 3 Preparation of 4-dimethylsilylphenol

To a cold solution (˜9° C.) of 26.0 g of4-dimethylsilylphenoxydimethylsilane in 250 ml of diethylether was added10 ml of a solution of sodium methoxide (0.4 N) in methanol and themixture stirred overnight. Solvents were removed by evaporation on arotary evaporator at room temperature to yield 15.6 g (83.0%) of crudeproduct, m.p. 59°-60° C. After recrystallization from hexane, the phenolwas obtained as needles, m.p. 61° C.

Calcd for C₈ H₁₂ SiO: C, 63.09; H, 7.95; Si, 18.44; mol. wt. 152.27.Found: C, 62.92; H, 8.01; Si, 18.52; mol. wt. 164 (VPO).

nmr: δ, o, (d, 6, SiCH₃); 4.1 (m, 1.6, SiH and φOH); 6.3-7.17 (m, 4,φH).

STEP 4 Preparation of bis(4-dimethylsilylphenyl)carbonate

To a cold (˜-21° C.) solution of 60.5 g. (0.40 mol.) of4-dimethylsilylphenol, 100 ml of pyridine and 500 ml of toluene, wasadded slowly 28.0 g (0.28 mol.) of phosgene in 300 ml of toluene. Afterthe addition was complete, the cooling bath was removed and the reactionmixture was stirred overnight. The pyridine salt formed was removed byfiltration and the filtrate washed three times with aqueous sodiumchloride solution. The organic layer was dried over anhydrous magnesiumsulfate and concentrated on a rotary evaporator. Upon cooling of theresidue, there was obtained 53.0 g (79.8%) of crude product. Thecarbonate was recrystallized from hexane to yield crystals, m.p. 72°-73°C.

Calcd. for C₁₇ H₂₂ Si₂ O₃ : C, 61.48; H, 7.15; Si, 16.91; mol. wt.332.09. Found: C, 61.27; H, 6.77; Si, 17.03; mol. wt. 334 (VPO).

nmr: 0 (d, 6, SiCH₃); 4.1 (septet, 0.9, ASiH); 7.03 (m, 4.1, φH).

STEP 5 Preparation of bis(4-hydroxydimethylsilylphenyl)carbonate

To a cold (˜0° C.) solution of 14.0 g ofbis(4-dimethylsilylphenyl)carbonate in 200 ml. of distilledtetrahydrofuran and 25 ml of water was added slowly 15.0 g of silveracetate accompanied by vigorous stirring. After the addition wascomplete, the solution was stirred at 0° C. overnight. The solid formedwas removed by filtration and the filtrate washed with saturated sodiumchloride solution until no acid was detected. The organic layer, driedover anhydrous magnesium sulfate and concentrated on a rotary evaporatorto a thick liquid, solidified upon standing. There was obtained 13.0 g(84.6%) of the expected product, m.p. 93°-4° C. The pure compound wasobtained by recrystallization from benzene and hexane solution, m.p.106° C.

Calcd. for C₁₇ H₂₂ Si₂ O₅ : C, 56.32; H, 6.12; Si 15.50; mol. wt.362.53. Found: C, 56,89; H, 6.31; Si 15.00; mol. wt. 361 (VPO),

nmr: δ, 0 (s, 11.4, SiCH₃); 1.3 (s, 2, OH); 6.8-7.3 (m, 8.2 φH).

Where it is desired to prepare very specialized carbonate-containingarylene bis-silanols, viz., disiloxanyl-type phenyl carbonate monomers,the below indicated STEPS 6 and 7 are conducted. In other words, STEPS 6and 7 are extensions of the basic 5-step procedure.

STEP 6 Preparation of bis[4-(1,1,3,3tetramethyldisiloxanyl)phenyl]carbonate

To a cold (0° C.) solution of 15.0 g (0.04 mol) ofbis(4-hydroxydimethylsilyl)phenylcarbonate in 75 ml. of toluene and 45ml. of triethylamine was added 12.0 g (0.13 mol) ofdimethylchlorosilane. After the addition was complete, the mixture wasstirred overnight. The solid was removed by filtration and the filtratewashed with water, dried over anhydrous magnesium sulfate andconcentrated on a rotary evaporator. Vacuum distillation of the residueat 170°-174° C./0.10 mm gave 16.5 g (84%) of the product.

Calcd. for C₂₁ H₃₄ Si₄ O₅ : C, 52.68; H, 7.16, Si, 23.46; mol. wt.478.80. Found: C, 52.87; H, 7.27, Si, 23.46; mol wt. 470 (VPO).

nmr: δ, 0-0.2 (d, s, 24, HSiCH₃), φSiCH₃) 5.16-4.66 (m, 2, SiH); 7.9-7.2(m, 8.2, φH).

STEP 7 Preparation ofbis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate

To a cold (-5° C.) solution of 100 ml of acetone, 4 ml. of water and acatalytic amount of 5% palladium-on-carbon was added slowly 9.0 g ofbis[4-(1,1,3,3-tetramethyldisiloxanyl) phenyl]carbonate in 20 ml. ofacetone over a period of 8 hrs. After the addition was complete, thepalladium-on-carbon was removed by filtration. The filtrate wasconcentrated on a rotary evaporator at room temperature to a viscousliquid which solidified upon treatment with pentane. There was obtained7.5 g (78%) of the required compound. The carbonate was recrystallizedfrom benzene and hexane solution to yield the pure compound, m.p.62°-63° C.

Calcd for C₂₁ H₃₄ Si₄ O₇ : C, 49.38; H, 6.71; Si, 21.99; mol. wt.510.80. Found: C, 49.44; H, 6.81, Si, 22.11; mol. wt. 502 (VPO).

nmr: δ, 0 (s, 12, SiCH₃); 0.24 (s, 12, SiCH₃); 1.8 (b, 2, OH); 7.3 (m,10, φH).

STEP 8 Polymerization ofbis[4-(1-hydroxy-1,1,3,3,-tetramethyldisiloxanyl)phenyl]carbonate

Bis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate (3.0 g)and 10 ml. of freshly-distilled pyridine were placed in 50-ml.round-bottomed flask, equipped with a magnetic stirring bar, a gas inlettube which extended just above the reaction mixture, and a gas outletleading into a sodium hydroxide solution. With the mixture stirredvigorously and cooled by an ice-water bath, phosgene was introducedslowly into the flask. A solid was formed in a few minutes and thesolution became viscous and caked. Excess phosgene was then removed bysweeping the system with nitrogen. The reaction mixture was diluted withdichloromethane and stirred until the solid formed was loosened. Thesolution was concentrated to a small volume on a rotary evaporatorbefore precipitating the polymer from methanol.

The equations shown herein below are included to illustrate thereactions which occur in each of the above enumerated STEPS 1 to 8,inclusive, described herein above. The number to the right of theequation corresponds to the step previously described which is involvedin the synthesis and polymerization of the included compounds. ##STR6##

PROCESS OBSERVATIONS

The Grignard reaction shown in equation 2 above was conducted in situwith excess dimethylchlorosilane and magnesium in tetrahydrofuransolvent. The conventional method for conducting such Grignard reactionsinvolves initial formation of the Grignard reagent, followed by acoupling reaction with dimethylchlrosilane. However, such conventionalmethod was found to be inadequate for complete converstion ofbromophenoxydimethylsilane to the dimethylsilylphenoxydimethylsilane.The bromophenoxydimethylsilane, if present in the product when theconventional method was involved, could not be removed by distillation.Hydrolysis of dimethylsilylphenoxydimethylsilane was carried out byintroducing water into the mixture of the silane and methanol. It hasbeen discovered that this particular order of addition must be followedor otherwise an undesirable rearrangement to the siloxybenzene (as shownby the following equation) will occur and there will be obtained animpure dimethylsilylphenol. ##STR7##

Pyridine was found to be the preferred acid-acceptor reagent forphosgenation of the phenol in the reaction shown in Equation 4. Althoughtriethylamine has been used in many similar reactions, it reacts withphosgene even at low temperatures. The product formed was found to bedifficult to remove, especially frombis[(3-dimethylsilyl)phenyl]carbonate.

Pure bis-silanols could not be isolated readily if any impurities werepresent. The oxidation of the silicon-hydrogen bond of the silyl hydrideto a silicon-hydroxy bond could be achieved either by the use of silveracetate or mercuric acetate in wet tetrahydrofuran or acetone solutionor by utilization of the method of G. H. Barnes, Jr., et al., aspublished in the Journal of Organic Chemistry 31, 885 (1966). TheBarnes, et al., method involves use of palladium-on-carbon catalyst inwet polar solvents.

In certain of the procedures described in accordance with thisinvention, water and acetone were employed as the solvent system. Theuse of this solvent pair requires careful control over the reactionconditions as described herein above. They should be closely followedand precisely controlled in order to obtain the desired products in ahighly pure condition.

Siloxane-containing bis-silanols can be prepared in the above indicatedstepwise manner by initial synthesis of the siloxane-containinghydrosilanes as illustrated in Equation 6 above, followed by theiroxidation to bis-silanols, as indicated in Equation 7 above.

Polymerization of carbonate-containing silanols has heretofore beenextremely difficult to conduct, and in most cases cannot be effected, byconventional heterocondensation of bis-silanols with diaminosilanes orby homocondensation reactions propagated by alkali reagents. Under thesereaction conditions, the carbonate linkages readily decompose and forman undesired mixture of products. This degradation does not occur inaccordance with the synthesis and polymerization procedures of thisinvention which permit the synthesis of carbonate-containing siloxanesof high molecular weight by treating bis-silanols with phosgene inpyridine solution at low ambient temperatures.

Although the mechanism of the polymerization reaction with respect tothe role of phosgene has not been fully elucidated, it appears that thespeed of the reaction is dependent on the reactivities of the respectivesilanols. It has been noted that bis-silanols wit hydroxysilyl groupsattached directly to the phenylene groups, such as bis[4(or3-hydroxydimethylsilyl)phenyl]carbonate, reacted rapidly in the presenceof phosgene and the polymerization was complete within several minutes.On the other hand, for bis[4(or3)-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate, thereaction was much slower and it was necessary to react this monomer inthe presence of phosgene until the solution became viscous and caked.The polymers obtained herein were all analyzed and characterized byconventional polymeric analysis and characterization procedures.

Five new bis-silanol monomers have been synthesized in highly purifiedform and polymerized by use of phosgene and pyridine in accordance withthis invention. They are: (1)bis(4-hydroxydimethylsilylphenyl)carbonate; (2)bis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate; (3)bis(3-hydroxydimethylsilylphenyl)carbonate; (4)bis[3-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate and (5)bis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)]benzene. As will beapparent to those skilled in the art, monomers (1) through (4) alreadycontain the carbonate linkage and, upon polymerization in accordancewith this invention, will result in polymers retaining the carbonatelinkage in the polymer backbone. Monomer (5), however, does not containa carbonate linkage and its polymers do not contain the carbonatelinkage upon homopolymerization.

This invention will be illustrated in additional detail in the exampleswhich follow. In these examples, all parts, percents and ratios are byweight unless otherwise indicated.

EXAMPLE 1 Preparation of Bis(4-hydroxydimethylsilylphenyl)carbonate

This monomer was prepared in accordance with the detailed procedures setforth above in STEPS 1 through 5 to yield 13.0 g. (84.6%) of theexpected product, m.p. 93°-4° C. The pure compound was obtained byrecrystallization from benzene and hexane solution, m.p. 106° C.

Calcd for C₁₇ H₂₂ Si₂ O₅ : C, 56.32; H, 6.12; Si 15.50; mol wt. 362.53.Found: C, 56.89; H, 6.31; Si 15.00; mol. wt. 361 (VPO).

nmr: δ, 0 (s, 11.4, SiCH₃); 1.3 (s, 2, OH); 6.8-7.3 (m, 8.2, φH).

This monomer is useful in forming high molecular weightpolysiloxanylenearylenecarbonate polymers which can be used as hightemperature resistant interlayers when cured and laminated to glass orpolycarbonate sheets according to laminating procedures well known inthe art.

EXAMPLE 2 Preparation of Bis(3-hydroxydimethylsilylphenyl)carbonate

This new monomer was prepared from the starting material3-dimethylsilylphenoxydimethylsilane (obtained in accordance with thesynthesis procedure of STEPS 1 and 2 above except for using3-bromophenoxydimethyldisilane in place of the corresponding 4-bromocompound of STEP 1).

To a solution of 122.1 g of 3-dimethylsilylphenoxydimethylsilane and 250ml. of methanol was added 35.5 ml of distilled water. After the mixturewas stirred overnight, the methanol was removed by evaporation at roomtemperature on a rotary evaporator. The concentrated solution wastreated with toluene, dried over anhydrous magnesium sulfate and againevaporated on a rotary evaporator to yield 89.85 g. of the desired3-dimethylsilylphenol.

To a cold (˜-20° C.) solution of 60.5 g (0.40 mol.) of3-dimethylsilylphenol, 100 ml of pyridine and 500 ml of toluene wasadded slowly 28.0 g. (0.28 mol.) of phosgene in 300 ml. of toluene.After the addition was complete, the cooling bath was removed and thereaction mixture was stirred overnight. The pyridine salt formed wasremoved by filtration and the filtrate washed three times with aqueoussodium chloride solutin, dried over anhydrous magnesium sulfate andevaporated on a rotary evaporator. The desired materialbis(3-dimethylsilylphenyl)carbonate was obtained by vacuum distillationas a liquid having a boiling point of 143° C./0.12 mm.

Calcd. for C₁₇ H₂₂ Si₂ O₃ : C, 61.48; H, 7.15; Si, 16.91; mol. wt.332.09. Found: C, 61.27; H, 6.77; Si, 17.03; mol. wt. 334 (VPO).

nmr. δ, 0 (d, 6, SiCH₃); 4.1 (septet, 0.9, Si--H); 7.03 (m, 4.1, φH).

To a cold (-5° C.) solution of 1000 ml. of acetone, 40 ml. of water and0.4 g. of 5% palladium-on-carbon was added slowly 84.0 g ofbis(3-dimethylsilylphenyl)carbonate in 200 ml. of acetone over a periodof 8 hrs. After the addition was complete, the palladium-on-carbon wasremoved by filtration. The filtrate was concentrated on a rotaryevaporator at room temperature to viscous liquid which solidified upontreatment with pentane. There was obtained 69.0 g (93.2%) of the desiredcompound. The carbonate was recrystallized from a mixture of chloroformand pentane to yield crystals, m.p. 94°-95° C.

Calcd. for C₁₇ H₂₂ Si₂ O₅ : C, 56.32; H, 6.12; Si, 15.50; mol. wt.362.53. Found: C, 56.08; H, 5.90; Si, 15.59; mol. wt. 362 (MS).

nmr: δ, 0 (s, 12, SiCH₃); 2.5 (b, 1.6, OH); 7.09-7.45 (m, 8, φH).

This monomer is likewise useful in forming high molecular weightpolysiloxanylenearylenecarbonates for utilization as high-temperaturetransparent interlayers.

EXAMPLE 3 Preparation ofBis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate

By use of the procedure of Example 2, utilized for the preparation ofbis(3-hydroxydimethylsilylphenyl)carbonate, 9.0 g ofbis[4-(1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate gave 7.5 g (78% )of the required compound. The carbonate was recrystallized from benzeneand hexane solution to yield the pure compound,bis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl) phenyl]carbonate, m.p.62°-63° C.

Calcd. for C₂₁ H₃₄ Si₄ O₇ : C, 49.38; H, 6.71; Si, 21.99; mol. wt.510.80. Found: C, 49.44; H, 6.81, Si, 22.11; mol. wt. 502 (VPO).

nmr: δ, 0 (s, 12, SiCH₃); 0.24 (s, 12 SiCH₃); 1.8 (b, 2, OH); (m, 10φH).

This new monomer is useful to prepare the corresponding high molecularweight siloxanylenearylenecarbonate polymer, which is useful as a hightemperature-resistant transparent interlayer material.

EXAMPLE 4 Preparation ofBis[3-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate

To a cold (0° C.) solution of 15.0 g (0.041 mol.) ofbis(3-hydroxydimethylsilylphenyl)carbonate in 75 ml. of toluene and 45ml. of triethylamine was added 12.0 g (0.13 mol.) ofdimethylchlorosilane. After the addition was complete, the mixture wasstirred overnight. The amine salt formed was removed by filtration andthe filtrate washed three times with aqueous sodium chloride solution.The organic layer was dried over anhydrous magnesium sulfate andconcentrated on a rotary evaporator.Bis[3-(1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate was obtained as aliquid boiling at 164° C./0.10 mm. in a yield of 17 g. (73%).

Calcd. for C₂₁ H₃₄ Si₄ O₅ : C, 52.68; H, 7.16, Si, 23.46; mol. wt.478.80. Found: C, 52.87; H, 7.27, Si, 23.46; mol. wt. 470 (VPO).

nmr: δ, 0-0.2 (d, s, 24, HSiCH₃, φSiCH₃) 5.16-4.66 (m, 2, SiH) 7.9-7.2(m, 8.2, φH).

The bis[3-(1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate was thenconverted to the corresponding hydroxy compound by reaction with acetoneand water in the presence of palladium-on-carbon catalyst (as per thelatter stage of EXAMPLE 2) to the desiredbis[3-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate, whichwas isolated as a liquid.

Calcd. for C₂₁ H₃₄ Si₄ O₇ : C, 49.38; H, 6.74; Si, 21.99; mol. wt.510.80. Found: C, 50.33; H, 6.59; Si 21.27; mol. wt. 510 (MS).

nmr: δ, 0 (s, 12, SiCH₃); 0.18 (s, 12, SiCH₃); 3.6 (b, 3.2, OH);7.09-7.39 (m, 8, φH).

EXAMPLE 5

To a cold solution of 51.0 g. (0.225 mol.) of1,4-bis(hydroxydimethylsilyl)benzene in 300 ml. of dry toluene and 200ml of distilled pyridine was added 66.0 g. (0.7 mol) ofdimethylchlorosilane. After the addition was complete the mixture wasstirred overnight. The pyridine salt was removed by filtration and thefiltrate was washed three times with sodium chloride solution. Theorganic layer was dried over anhydrous magnesium sulfate, concentratedon a rotary evaporator and vacuum distilled. Thebis[4-(1,1,3,3-tetramethyldisiloxanyl)]benzene was distilled at 62°-63°C./0.02 mm.

The bis[4-(1,1,3,3-tetramethyldisiloxanyl)]benzene was then converted tothe correspondingbis[4-(1-hydroxy-1,1,3,3-tetramethyl-disiloxanyl)]benzene by the methoddescribed in Example 2. The desired compound melted at 89°-91° C.

This new monomer is useful in forming high molecular weightpolysiloxanylenearylene polymers for utilization as high-temperatureelastomers.

EXAMPLE 6 Polymerization of Bis(4-hydroxydimethylsilylphenyl)carbonate

Bis(4-hydroxydimethylsilylphenyl)carbonate (3.0 g, 0.0081 mol.) and 30ml of freshly-distilled pyridine were placed in a 50 ml. round-bottomedflask, equipped with a magnetic stirring bar, a gas inlet tube (whichextended just above the reaction mixture), and a gas outlet leading intoa sodium hydroxide solution. With the mixture stirred vigorously andcooled by an ice-water bath, phosgene was introduced slowly into theflask. A solid was formed in a few minutes and the solution becameviscous and caked. Excess phosgene was then removed by sweeping thesystem with nitrogen. The reaction mixture was diluted withdichloromethane and stirred until the solid formed was partiallyliquified. The mixture was then poured into methanol and the new polymerpurified by redissolving the precipitate in dichloromethane,reprecipitating in methanol four times and drying at 90° C. in vacuumfor 24 hours.

The resulting polysiloxanylenearylenecarbonate was obtained in 80percent yield and has the structure: ##STR8##

This new polymer had the analyses and characteristics tabulated below inTABLE 1.

                  TABLE 1                                                         ______________________________________                                        η Tg                   Analyses (Calcd.) & Found                          (dl/g)                                                                              (°C.)                                                                           NMR         C, %   H, %  Si, %                                 ______________________________________                                        1.75  49     δ, 0 (s, 12, SiCH.sub.3)                                                              59.05  5.73  16.29                                              7.03, (m, 8, φH)                                                                        (59.27)                                                                              (5.85)                                                                              (16.30)                               ______________________________________                                    

As a general rule, it is recognized in the art that polysiloxanes havinga viscosity of 1.0 dl/g and greater have a molecular weight (numberaverage) of at least about 100,000. This new polymer, having a viscosityof 1.75 dl/g has a molecular weight well in excess of 100,000.

The polymer is useful as a precursor for the development of aheat-stable elastomeric plastic interlayer material upon curing inaccordance with known curing techniques.

EXAMPLE 7 Polymerization of Bis(3-hydroxydimethylsilylphenyl)carbonate

The polymerization procedure of EXAMPLE 6 was repeated except for usingthe new monomer bis(3-hydroxydimethylsilylphenyl)carbonate. Thecorresponding polysiloxanylenearylenecarbonate was obtained in 47percent yield and has the structure: ##STR9##

This new polymer had the analyses and characteristics tabulated below inTABLE 2.

                  TABLE 2                                                         ______________________________________                                        η Tg                   Analyses (calcd.) & Found                          (dl/g)                                                                              (°C.)                                                                           NMR         C, %   H, %  Si, %                                 ______________________________________                                        1.30  14     δ, 0 (S, 12, SiCH.sub.3)                                                              59.29  5.87  16.33                                              6.90-7.10 (m, 8, φH)                                                                    (59.27)                                                                              (5.85)                                                                              (16.30)                               ______________________________________                                    

This new polymer is useful as a high-temperature transparent interlayerwhen cured.

EXAMPLE 8 Polymerization of Bis(hydroxydimethylsilyl)benzene

The polymerization procedure of EXAMPLE 6 was repeated except usingbis(hydroxydimethylsilyl)benzene as monomer. The correspondingpolysiloxanylene arylene polymer was obtained in 92 percent yield andhas the structure: ##STR10##

This new polymer had the analyses and characteristics set forth in TABLE3.

                  TABLE 3                                                         ______________________________________                                        η Tg                   Analyses (Calcd.) & Found                          (dl/g)                                                                              (°C.)                                                                           NMR         C, %   H, %  Si, %                                 ______________________________________                                        1.75  -23    δ, 0 (s, 12, SiCH.sub.3)                                                              57.31  7.90  27.43                                              7.20 (s, 4, φH)                                                                         (57.63)                                                                              (7.74)                                                                              (26.96)                               ______________________________________                                    

This polysiloxanylenearylene polymer when cured is useful as a basematerial for the formulation of heat resistant elastomers.

EXAMPLE 9 Polymerization of 4,4'-Bis(hydroxydimethylsilyl)diphenyl ether

The polymerization procedure of EXAMPLE 6 was repeated except for using4,4'-bis(hydroxydimethylsilyl)diphenyl ether as the monomer. Theresulting polysiloxanylenearylene polymer was obtained in 55 percentyield and has the structure: ##STR11##

This new polymer was analyzed and has the analyses and characteristicsshown in TABLE 4.

                  TABLE 4                                                         ______________________________________                                        η Tg                    Analyses (Calcd.) & Found                         (dl/g)                                                                              (°C.)                                                                            NMR         C, %  H, %   Si, %                                ______________________________________                                        1.35  17      δ, 0 (s, 12, (SiCH.sub.3))                                                            64.05 7.01   18.75                                              6.55-6.75 (d, 4, φOH)                                                     7.05-7.25 (d, 4, SiφH)                                                                  (63.95)                                                                             (6.71) (18.70)                              ______________________________________                                    

This new polymer is useful for the fabrication of high-temperatureelastomers when cured.

EXAMPLE 10 Polymerization of3,5-Bis[hydroxymethyl(3,3,3-trifluoropropyl)silyl]trifluoromethylbenzene

The polymerization procedure of EXAMPLE 6 was repeated except for using3,5-bis[hydroxymethyl(3,3,3-trifluoropropyl)silyl]trifluoromethylbenzeneas monomer. The corresponding trifluoropropylsiloxanylenephenylenepolymer was obtained in 43 percent yield and has the structure:##STR12##

The analytical data and characteristics for this new polymer are setforth in TABLE 5.

                  TABLE 5                                                         ______________________________________                                        η Tg                    Analyses (Calcd.) & Found                         (dl/g)                                                                              (°C.)                                                                            NMR         C, %  H, %   Si, %                                ______________________________________                                                      δ, 0-0.55                                                 1.06  -13     (d, 7, CH.sub.2 SiCH.sub.3)                                                                 42.48 4.25   35.47                                              0.9-1.1 (m, 4, CH.sub.2)                                                      7.94 (s, 2, φH)                                                           8.12 (s, 1, φH)                                                                         (40.90)                                                                             (3.89) (12.15)                              ______________________________________                                    

This new polymer is useful as a base material for the formulation of ahigh-temperature stable aircraft fuel tank sealant.

EXAMPLE 11 Polymerization of a,a'Bis(dimethylhydroxysilyl)-m-xylene

The polymerization procedure of EXAMPLE 6 was repeated except for usinga,a'-bis(dimethylhydroxysilyl)-m-xylene as monomer. The correspondingpolysiloxanylenealkarylene polymer was secured in 75 percent yield andhas the structure: ##STR13##

The analytical results and characteristics for this new polymer aregiven in TABLE 6.

                  TABLE 6                                                         ______________________________________                                        η Tg                   Analyses (Calcd.) & Found                          (dl/g)                                                                              (°C.)                                                                            NMR        C, %   H, %  Si, %                                 ______________________________________                                        1.02  -41     δ, 0 (s, 12, SiCH.sub.3)                                                             61.16  8.46  23.65                                               2.03 (s, 4, CH)                                                               6.4-6.9 (m, 4, φH)                                                                     (60.96)                                                                              (8.53)                                                                              (23.76)                               ______________________________________                                    

This polymer is useful for the development of heat-resistant elastomersfor aerospace applications.

EXAMPLE 12 Polymerization ofBis[3-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate

The polymerization procedure of EXAMPLE 6 was followed except for usingthe present monomer and except for the fact that the reaction mixturewas made more concentrated by dissolving bis-silanol (3.0 g) in 10 ml offreshly-distilled pyridine. The reaction mixture, after having beentreated with phosgene, was shaken with dichloromethane until a solutionwas obtained. The solution was concentrated to a small volume on arotary evaporator before precipitating the polymer from methanol. Theresulting polymer was obtained in 54% yield and has the structure:##STR14##

The analytical data and characteristics for this new polysiloxanylenearylene carbonate polymer are set forth in TABLE 7.

                  TABLE 7                                                         ______________________________________                                        η Tg                   Analyses (Calcd.) & Found                          (dl/g)                                                                              (°C.)                                                                            NMR        C, %   H, %  Si, %                                 ______________________________________                                        1.18  -35     δ, 0 (s, 12, SiCH.sub.3)                                                             50.90  6.74  22.83                                               0.28 (s, 12, SiCH.sub.3)                                                      7.31 (m, 8, φH)                                                                        (51.18)                                                                              (6.54)                                                                              (22.80)                               ______________________________________                                    

This new polymer is useful when cured for preparation of heat-resistanttransparent interlayers for aircraft windshield and canopy assemblies.

EXAMPLE 13

Nine weight parts of the monomer of Example 12 was copolymerized withone weight part ofbis[3-(1-hydroxy-1-vinyl-1,3,3-trimethyldisiloxanyl)phenyl]carbonate toyield the desired copolymer having a viscosity of 1.2 dl/g. and atransition temperature, Tg, of -37° C. This copolymer is useful as areadily curable transparent interlayer material, curable in accordancewith known procedures, e.g., peroxide curing systems, and has thestructure: ##STR15##

EXAMPLE 14 Polymerization ofBis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate

That polymerization procedure of EXAMPLE 12 was followed except that thesubject monomer was used rather than the analogous meta-substitutedmonomer of EXAMPLE 12. The resulting homopolymer was obtained in 77percent yield and has the structure: ##STR16##

The analytical data and characteristics for this newpolysiloxanylenearylenecarbonate polymer are shown in TABLE 8.

                  TABLE 8                                                         ______________________________________                                        η Tg                   Analyses (Calcd.) & Found                          (dl/g)                                                                              (°C.)                                                                             NMR       C, %   H, %  Si, %                                 ______________________________________                                        1.40  -24      δ, 0-0.25                                                               (s, s, 25, SiCH.sub.3)                                                                    51.17  6.76  22.56                                                7.32 (m, 8, φH)                                                                       (51.18)                                                                              (6.54)                                                                              (22.80)                               ______________________________________                                    

This new polymer is useful as the curable base material for hightemperature transparent interlayers.

EXAMPLE 15 Polymerization of1,4-Bis(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)benzene

The polymerization procedure of EXAMPLE 12 was repeated except that thesubject monomer was employed. The resulting siloxanylenearylene polymerwas obtained in 84 percent yield and has the structure: ##STR17##

The analytical data and characteristics for this new polymer are setforth in TABLE 9.

                  TABLE 9                                                         ______________________________________                                        η Tg                   Analyses (Calcd.) & Found                          (dl/g)                                                                              (°C.)                                                                            NMR        C, %   H, %  Si, %                                 ______________________________________                                        1.60  -77     δ, 0 (s, 12, SiCH.sub.3)                                                             47.55  8.41  31.47                                               0.28 (s, 12, SiCH.sub.3)                                                      7.48 (m, 4, φH)                                                                        (47.14)                                                                              (7.91)                                                                              (31.50)                               ______________________________________                                    

This new polymer is useful as a readily curable thermally stableelastomer for aerospace applications such as an interlayer, tanksealant, etc.

We claim:
 1. Bis(3-hydroxydimethylsilylphenyl)carbonate having a meltingpoint of 94°-95° C. 2.Bis[4-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate. 3.Bis[3-(1-hydroxy-1,1,3,3-tetramethyldisiloxanyl)phenyl]carbonate.